Method for fabricating solid state electrochromic device, solid state electrochromic device and its applications

ABSTRACT

An electrochromic apparatus includes a first glass, a first adhesive layer disposed on the first glass, a second glass, a second adhesive layer disposed on the second glass, a solid-state electrochromic device (ECD) interposed between the first adhesive layer and the second adhesive layer, and a sealant disposed at edges of the first glass and the second glass to seal the ECD. The first adhesive layer and the second adhesive layer are disposed between the first glass and the second glass. The first adhesive layer and the second adhesive layer are optically transparent. Edges of the adhesive layers are flush with or beyond edges of the ECD. The sealant is adhesive and waterproof.

REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part application of U.S.patent application Ser. No. 16/942,070 filed Jul. 29, 2020, which is acontinuation of International Application No. PCT/US2019/051112 filed onSep. 13, 2019, which claims priority to U.S. Provisional Application No.62/730,977 filed on Sep. 13, 2018, U.S. Provisional Application No.62/839,419 filed on Apr. 26, 2019, U.S. Provisional Application No.62/839,431 filed on Apr. 26, 2019, U.S. Provisional Application No.62/849,808 filed on May 17, 2019, U.S. Provisional Application No.62/849,810 filed on May 17, 2019, U.S. Provisional Application No.62/852,050 filed on May 23, 2019, and U.S. Provisional Application No.62/861,399 filed on Jun. 14, 2019. The entire contents of all of theabove-referenced applications are incorporated herein by reference.

TECHNICAL FIELD

The present disclosure is related to methods for fabricating solid stateelectrochromic devices, solid state electrochromic devices, andapplications of the solid state electrochromic devices.

BACKGROUND

Electrochromic devices (ECDs) has drawn a lot of interest due to itspotential applications to improve functionality of homes and vehicles.Based on the use of electrolytes, ECDs can be categorized into differenttypes, including gel, liquid, and solid-state ECDs. During theassembling of ECDs using liquid or gel electrolytes, the workingelectrode (WE) and counter electrode (CE) need to be separated by aspacer with the electrolyte filled into a gap between them. The cavityis then sealed by epoxy. To prevent leakage of the electrolytes from theliquid or gel-based ECDs, complicated sealing and edge designs arerequired. Although adding polymeric thickening agents (such as, PVA,PMMA, PVDF-HFP, etc.) to form gel electrolytes can minimize leakageissues, generally the total amount of the polymer matrix is below 20 wt.% to maintain the appropriate ionic conductivity. The majority of theelectrolyte layer still contains liquid or gel, and the mechanicrobustness remains a concern.

Solid state ECDs are desirable for many applications because theyprovide many advantages over liquid/gel-based ECDs including bettersafety, long lifetime, the possibility for roll to roll processing, etc.

SUMMARY

Described herein are solid state electrochromic devices, methods forfabricating solid state electrochromic devices, and applications for thesolid state electrochromic devices.

In one aspect, the disclosure describes an electrochromic device. Theelectrochromic device includes a first flexible substrate, a firsttransparent electrode disposed on the first flexible substrate, anelectrochromic layer disposed on the first transparent electrode, and asolid electrolyte layer disposed on the electrochromic layer. The solidelectrolyte layer contains less than 20 wt % of neutral small organicmolecules having a molecular weight of 3000 or less. The electrochromicdevice further includes an ion storage layer disposed on the solidelectrolyte layer, a second transparent electrode disposed on the ionstorage layer, and a second flexible substrate disposed on the secondtransparent electrode. In some embodiments, the solid electrolyte layercontains less than 10%, 5%, or 3% in weight of neutral small organicmolecules. In some embodiments, the solid electrolyte layer is free ofsmall organic molecules which cannot be detected by the knowninstruments.

In some embodiments, the first flexible substrate and the secondflexible substrate include one of polyethylene terephthalate, cyclicolefin copolymer, triacetate cellulose or among others now known orlater developed.

In some embodiments, the first transparent electrode and the secondtransparent electrode include indium-tin oxide (ITO), aluminum zincoxide (AZO), fluorine doped tin oxide (FTO), silver nanowires, graphene,carbon nanotube, metal mesh based transparent conductive electrodes,silver-nanoparticle ink or among others now known or later developed.

In some embodiments, the ion storage layer includes one or more oxidesof metal elements in Group 4-12 that are capable to store cations duringthe reduction reaction. Examples include, but are not limited to, oxidesof Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu, Zn, or any mixtureof these oxides or any one of these metal oxides doped by any othermetal oxides, e.g., Nb₂O₅ doped with 5 wt. % of TiO₂, among others nowknown or later developed. In some embodiments, the ion storage layerincludes a transition-metal complex. The transition-metal complexincludes, but is not limited to, one of Prussian green, Prussian white,Prussian brown or Tenshi blue Fe4[Fe(CN)₆]₃, ferrous oxide, ferricoxide, ferroferric oxide, KFeFe(CN)₆, FeNiHCF, FeHCF, NiHCF, Prussianblue nanoparticles, or NxMy{Fe(CN)₆} where M is a metal elementincluding Fe, Co, Ni, Mn, Zn, or Cu, among others now known or laterdeveloped, and N is an alkali metal ion. In some embodiments, the ionstorage layer includes one or more of redox-active polymers including,but not limited to, redox active nitroxyl or galvinoxyl radicalpolymers, or conjugated polymers. In some embodiments, the ion storagelayer includes composites of any of the transition-metal complexes andmetal oxides, transition-metal complexes and redox active polymers,metal oxides or redox active polymers.

In some embodiments, the electrochromic layer includes one or more ofWO₃, poly(decylviologen) and its derivatives, polyaniline and itsderivatives, all kinds of electrochromic conjugated polymers such aspolypyrrole and its derivatives, polythiophene and its derivatives,poly(3,4-ethylenedioxythiophene) and its derivatives,poly(propylenedioxythiophene) and its derivatives, polyfurane and itsderivatives, polyfluorene and its derivatives, polycarbazole and itsderivatives, and their copolymers, or their copolymers containing acertain ratio of acceptor units, such as benzothiadiazole,benzoselenadiazole, benzooxazole, benzotriazole, benzoimidazole,quinoxalines, and diketopyrrolopyrroles, and others now known or laterdeveloped.

In some embodiments, the solid electrolyte layer includes ion conductingpolymers copolymerized with monomers or oligomers, wherein the monomersor oligomers have plasticizing moieties as a side chain. In someembodiments, the solid electrolyte layer includes ion conductingpolymers chemically linked with plasticizing linear polymers that have aglass transition temperature less than −20° C. In some embodiments, thesolid electrolyte layer includes ion conducting polymers chemicallylinked with plasticizing polymer blocks that have plasticizing groups asside chains. In some embodiments, the solid electrolyte layer includesbrush copolymers having a main chain of soft polymers and side chains ofion-conducting species and one or more non-miscible groups. In someembodiments, additives with cross-linking functional groups can be addedto enhance the mechanical modulus of the solid electrolyte layer.

In another aspect, the disclosure describes a method for forming anelectrochromic device. The method includes coating a first flexiblesubstrate with a first transparent electrode; coating, on the firstflexible substrate, an electrochromic layer on the first transparentelectrode; coating a second flexible substrate with a second transparentelectrode; coating, on the second flexible substrate, an ion storagelayer on the second transparent electrode; providing a polymerelectrolyte solution or electrolyte precursor solution to a surface ofthe electrochromic layer, or to a surface of the ion storage layer, orto a surface of the electrochromic layer and a surface of the ionstorage layer, or to the gap between a surface of the electrochromiclayer and a surface of the ion storage layer; laminating the firstflexible substrate with the second flexible substrate such that an areaof one of the substrates is not covered by another one of thesubstrates; and curing the polymer electrolyte solution or theelectrolyte precursor solution interposed between the electrochromiclayer and the ion storage layer to form the electrochromic device.

In some embodiments, the method further includes removing materials fromthe first transparent electrode or the second transparent electrode atthe area. In some embodiments, the method further includes attaching acircuit to the area.

In some embodiments, the polymer electrolyte solution or the electrolyteprecursor solution is cured to generate an electrolyte layer having lessthan 20 wt % of neutral small organic molecules having a molecularweight of 3000 or less. In some embodiments, the polymer electrolytesolution or the electrolyte precursor solution is cured by pressing thecoated substrates to each other at a temperature higher than 90° C. at apressure of 30 MP-500 MP. In some embodiments, the polymer electrolytesolution or the electrolyte precursor solution may be cured at room(e.g., 1 atmosphere of pressure) temperature.

In some embodiments, the electrochromic layer is coated on the firstsubstrate or the ion storage layer is coated on the second substrate byany one of a variety of solution-compatible coating strategies,including spray coating, spin coating, slot-die coating, slit coating,roll-to-roll coating, micro-concave coating, screen printing, transfercoating, or wire bar coating, among others now known or later developed.Some of the inorganic materials can also be fabricated via sputteringmethod.

BRIEF DESCRIPTION OF THE DRAWINGS

Certain features of various embodiments of the present technology areset forth with particularity in the appended claims. A betterunderstanding of the features and advantages of the technology will beobtained by reference to the following detailed description that setsforth illustrative embodiments, in which the principles of the inventionare utilized, and the accompanying drawings of which:

FIG. 1 is a block diagram of an electrochromic device, according to oneexample embodiment.

FIG. 2 is a flow chart illustrating a method for forming anelectrochromic device, according to one example embodiment.

FIGS. 3A and 3B illustrate two lamination configurations in which anarea of one of the substrates is not covered by another one of thesubstrates, according to example embodiments.

FIG. 4 illustrates hexagonal electrochromic layer film and ion storagelayer film, according to one example embodiment.

FIG. 5 is a schematic diagram showing a method for dispensing aprecursor for electrolyte on an electrochromic layer using a wire barcoater, according to one example embodiment.

FIG. 6 is a schematic diagram showing that an ion storage layer isoverlaid on an electrolyte-coated electrochromic layer in a staggeredmanner, according to one example embodiment.

FIG. 7 is a schematic diagram showing a circuit for an electrochromicdevice, according to one example embodiment.

FIG. 8A illustrates rectangular electrochromic layer film and ionstorage layer film, according to one example embodiment.

FIG. 8B is a schematic diagram showing that the ion storage layer shownin FIG. 8A is overlaid on the electrolyte-coated electrochromic layershown in FIG. 8A in a staggered manner, according to one exampleembodiment.

FIG. 8C is a schematic diagram showing a circuit for the electrochromicdevice shown in FIG. 8B, according to one example embodiment.

FIG. 9 is a schematic diagram showing a roller press technique tolaminate an electrochromic layer film and an ion storage layer film withan electrolyte precursor dispensed therebetween, according to oneexample embodiment.

FIG. 10 is a diagram showing transmittance changes of the thin-film ECDsbent at different angles, according to one example embodiment.

FIGS. 11(A)-(E) are pictures showing ECDs in various operationsaccording to example embodiments.

FIG. 12 is a diagram showing transmittance change of an ECD with onesecond switching time, according to one example embodiment.

FIG. 13A is an explosive view of an anti-glare rearview mirrorcontaining a solid-state ECD, according to one example embodiment.

FIG. 13B is a schematic diagram illustrating a cross-section view of theanti-glare rearview mirror shown in FIG. 13A according to oneembodiment.

FIG. 13C is another schematic diagram illustrating a cross-section viewof the anti-glare rearview mirror shown in FIG. 13A according to anotherembodiment.

FIGS. 14A and 14B are schematic diagrams illustrating configurations tobend thin films for forming curved rearview mirrors, according toexample embodiments.

FIG. 15 is a diagram showing a process scheme for forming a rearviewmirror, according to one example embodiment.

FIGS. 16A and 16B are schematic diagrams illustrating rollers forpressing thin films for forming rearview mirrors, according to exampleembodiments.

FIG. 17 is a diagram showing another process scheme for forming arearview mirror, according to one example embodiment.

FIG. 18 is a diagram showing a process scheme for forming a rearviewmirror, according to one example embodiment.

FIG. 19 is a diagram showing another process scheme for forming arearview mirror, according to one example embodiment.

FIG. 20 is a diagram showing another process scheme for forming arearview mirror according to one example embodiment.

FIG. 21 is a schematic diagram showing a sealing process for forming arearview mirror, according to one example embodiment.

FIGS. 22A and 22B are schematic diagrams showing sealing processes forforming a rearview mirror, according to example embodiments.

FIG. 23 is a schematic diagram showing another sealing process forforming a rearview mirror, according to one example embodiment.

FIG. 24 is a schematic diagram showing layer structures of an ECDrearview mirror, according to one example embodiment.

DETAILED DESCRIPTION OF EMBODIMENTS

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments of theinvention. However, one skilled in the art will understand that theinvention may be practiced without these details. Moreover, whilevarious embodiments of the invention are disclosed herein, manyadaptations and modifications may be made within the scope of theinvention in accordance with the common general knowledge of thoseskilled in this art. Such modifications include the substitution ofknown equivalents for any aspect of the invention in order to achievethe same result in substantially the same way.

Unless the context requires otherwise, throughout the presentspecification and claims, the word “comprise” and variations thereof,such as, “comprises” and “comprising” are to be construed in an open,inclusive sense, that is as “including, but not limited to.” Recitationof numeric ranges of values throughout the specification is intended toserve as a shorthand notation of referring individually to each separatevalue falling within the range inclusive of the values defining therange, and each separate value is incorporated in the specification asit were individually recited herein. Additionally, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment of the present invention. Thus, the appearances of thephrases “in one embodiment” or “in an embodiment” in various placesthroughout this specification are not necessarily all referring to thesame embodiment, but may be in some instances. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments.

Various embodiments described herein are directed to all solid-stateECDs that use solid-state thin films for each of the working electrodeand counter electrode, which are then bonded together with ahigh-performance transparent solid-state electrolyte formed via in-situphoto- or thermal-crosslinking process. The all-solid-state thin-filmECDs of the present disclosure display great flexibility and can beadapted to virtually any curvature or shape. In some embodiments, a thinlayer (e.g., 5 μm which can be achieved using manufacturing-friendly andcost-efficient processes) of solid-state electrolyte can function asboth the ionic conductor and separator of the electrodes. Due to reducedneutral small organic molecules (for example, solvent, plasticizer,ionic liquid), ECDs of the present disclosure have more stableelectrolytes and electrode interfaces, resulting in a long-life cyclecompared to the liquid- or gel-based ECDs. In some embodiments, a smallvoltage (e.g., 1.5 V) may be able to drive the ECDs consistent with thepresent disclosure, which is beneficial for battery-poweredapplications.

Embodiments will now be explained with accompanying figures. Referenceis first made to FIG. 1. FIG. 1 is a block diagram of an electrochromicdevice 100, according to one example embodiment. The electrochromicdevice 100 includes a first flexible substrate 102, a first transparentelectrode 104 disposed on the first flexible substrate 102, anelectrochromic layer 106 disposed on the first transparent electrode104, a solid electrolyte layer 108 disposed on the electrochromic layer106, an ion storage layer 110 disposed on the solid electrolyte layer108, a second transparent electrode 112 disposed on the ion storagelayer 110, a second flexible substrate 114 disposed on the secondtransparent electrode 112, and a power supply 116 connected to the firsttransparent electrode 104 and the second transparent electrode 112. Insome embodiments, the solid electrolyte layer 108 contains less than20%, 10%, 5%, or 3% in weight of neutral small organic molecules havinga molecular weight of 3000 or less. In some embodiments, the solidelectrolyte layer 108 is free of the small organic molecules that can bedetected or measured by the known instruments. In some embodiments, thesolid electrolyte layer 108 may contain some organic counter ions ofnon-monomers/non-oligomers ingredients, such as lithium salts.

For convenience, in some instance in this disclosure, the combination ofthe first flexible substrate 102, the first transparent electrode 104,and the electrochromic layer 106 may be referred to as a workingelectrode (WE), and the combination of the second flexible substrate114, the second transparent electrode 112, and the ion storage layer 110may be referred to as a counter electrode (CE).

In some embodiments, the first flexible substrate 102 and the secondflexible substrate 114 may be transparent substrates. Example materialsfor the substrates 102 and 114 include polyethylene terephthalate,cyclic olefin copolymer, triacetate cellulose, or other suitablematerials now-known or later-developed. The flexible substrates 102 and114 allow the final ECDs to be bent to fit in various cases fordifferent applications, such as rear mirrors, windows, and sunroofs forvehicles or vessels. A thickness of the first flexible substrate 102 orthe second flexible substrate 114 may be 10 to 1000 μm.

In some embodiments, the first transparent electrode 104 and the secondtransparent electrode 112 may be thin film materials. Example materialsfor the transparent electrodes 104 and 112 may include indium-tin oxide(ITO), aluminum zinc oxide (AZO), fluorine doped tin oxide (FTO), silvernanowires, graphene, carbon nanotube, metal mesh based transparentconductive electrodes, silver-nanoparticle ink for reflective device, orother suitable materials now-known or later-developed. A thickness ofthe first transparent electrode 104 or the second transparent electrode112 may be 1 to 800 nm.

In some embodiments, the ion storage layer 110 may include oxides of themetal elements in Group 4-12 that are capable to store cations duringthe reduction reaction. Examples include oxides of Ti, V, Nb, Ta, Cr,Mo, W, Mn, Fe, Co, Jr, Ni, Cu, Zn, or any mixture of these oxides or anyone of these metal oxides doped by any other metal oxides, e.g., Nb₂O₅doped with 5 wt. % of TiO₂, or other suitable materials now-known orlater-developed.

In some embodiments, the ion storage layer 110 may includetransition-metal complexes that can undergo reduction reactions. Theexample metal complexes includes, but is not limited to, Prussian green,Prussian white, Prussian brown, Tenshi blue Fe4[Fe(CN)₆]₃, ferrousoxide, ferric oxide, ferroferric oxide, KFeFe(CN)6, FeNiHCF, FeHCF,NiHCF, Prussian blue nanoparticles, or inorganic compound of ironNxMy{Fe(CN)₆} where M is a metal element including Fe, Co, Ni, Mn, Zn,and Cu, among others now known or later developed and N is alkali metalion, such as Na, K, among others now known or later developed.

In some embodiments, the ion storage layer 110 may include redox-activepolymers that can store cations during the reversible reductionreaction. Example redox-active polymers may include, but not limited to,redox active nitroxyl or galvinoxyl radical polymers (e.g.,poly(nitronylnitroxylstyrene) and poly(galvinoxylstyrene)), andconjugated polymers (including polyaniline, PEDOT: PSS, polypyrrole,among the others now known or later developed).

In some embodiments, the ion storage layer 110 may include composites ofany combinations of the transition-metal complexes, metal oxides, andredox active polymers. A thickness of the ion storage layer 110 may be 1nm to 10 μm.

In some embodiments, the electrochromic layer 106 may include one ormore materials that can be reduced/oxidized and store counterions. Theelectrochromic layer 106 can be composed of one or more of the followingmaterials including WO₃, poly(decylviologen) and its derivatives,polyaniline and its derivatives, all kinds of electrochromic conjugatedpolymers such as polypyrrole and its derivatives, polythiophene and itsderivatives, poly(3,4-ethylenedioxythiophene) and its derivatives,poly(propylenedioxythiophene) and its derivatives, polyfurane and itsderivatives, polyfluorene and its derivatives, polycarbazole and itsderivatives, and their copolymers, or their copolymers containing acertain ratio of acceptor units, such as benzothiadiazole,benzoselenadiazole, benzooxazole, benzotriazole, benzoimidazole,quinoxalines, and diketopyrrolopyrroles, and others now known or laterdeveloped. A thickness of the electrochromic layer 106 may be 1 nm to 10μm.

In some embodiments, the solid electrolyte layer 108 has a thickness of0.1 um to 1000 μm. In some embodiments, the solid electrolyte layer 108can be formed from liquid materials cured by ultraviolet (UV) light orthermal exposure, changing from liquid to solid state in the curingprocess. The solid electrolyte layer 108 has good ionic conductivity andstability at a high temperature over 90° C. (e.g., for the defoamprocess and applications). Utilizing the solid electrolyte layer 108 inthe ECD 100 overcomes a series of problems that liquid or gelelectrolytes have such as being easy to leak, unstable, and difficult toprocess, and has advantages in production and process as well as safetyperformance.

For ECDs, the solid electrolyte is required to be transparent. Also,suitable solid electrolytes for ECDs need to be highly conductive totransfer ions between the ion storage layer and electrochromic layer.The present disclosure proposes a solid electrolyte with hightransparency, decent ion conductivity (e.g., >10⁻⁶ S/cm), and highstability.

Conventionally, solid electrolytes have been mostly developed forlithium ion batteries. These electrolytes are generally not suitable forelectrochromic devices because electrochromic devices require theelectrolytes to be highly transparent, which is not the case for mostsolid electrolytes. Over the few available examples of transparent solidelectrolytes for electrochromic devices, there are generally two types.The first type is inorganic solid electrolytes, such as lithiumphosphorus oxynitride (LiPON). However, the ion conductivity of LiPON istoo low (e.g., 10⁻⁷ S/cm) and LiPON can only be processed by high vacuumsputtering. The second type of solid electrolytes is composed ofpolymers blended with plasticizers. For examples, by blendingpolyethylene oxide (PEO) with succinonitrile and lithium salt, a solidelectrolyte with ion conductivity as high as 10⁻⁴ S/cm can be achieved.However, during the operation process, plasticizers in the conventionsolid electrolyte materials can easily penetrate into the electrochromiclayers and damage the device.

The present disclosure provides, among other things, a new solution inthe design of solid electrolytes in which the plasticizing moieties arecovalently linked onto ion-conducting polymers to form suitable solidelectrolytes for electrochromic devices. The typical ion-conductingpolymers such as PEO tend to crystallize, leading to the decrease oftransparency and ion conductivities. By introducing plasticizingmoieties into the ion-conducting polymers, the ordered packing of thepolymer chains are disturbed to suppress crystallization. Therefore, thetransparency and ion conductivities of the polymers can be greatlyenhanced, resulting in suitable electrolytes for ECDs. The plasticizingmoieties can be small molecular groups or soft polymer chains. Sincethese moieties are covalently linked to the polymer chains, they do notpenetrate into other layers of ECDs. The proposed polymer electrolytecan have high ion conductivity, high transparency, and good stability.

In some embodiments, the solid electrolyte layer 108 may include ionconducting polymers copolymerized with monomers or oligomers, where themonomers or oligomers have plasticizing moieties as a side chain. Insome embodiments, plasticizing moieties are small molecular groupslinked to the side chain of a monomer or oligomer, which can furthercopolymerize with ion conducting polymers into solid electrolytes.Example polymer electrolytes may include, but be not limited to:

wherein each of x, y, and z is an integer greater than 0, and

In some embodiments, the connection between different parts of mainchain, the connection between main chain and plasticizing groups (PR),the connection between main chain and cross-linking groups (CL) may beany type of one or several organic bonds.

Example PR groups may include, but is not limited to:

Generally, any function chemicals that can connect with two or moremonomers can be used as CL groups, including, but not limited to:

In some embodiments, to form these polymers, monomers or oligomers withthe plasticizing groups as side groups are first synthesized. Thesemonomers or oligomers are further linked with ion-conducting polymersthrough chain-end reactions. These plasticizing groups can reduce thecrystallinity of the ion conducting polymers, enhance the ionconductivity, and improve the transparency of the polymer electrolyte.Since the addition of the plasticizing groups may also decrease themechanical modulus of the polymers electrolytes, cross-linking partsmight also be added to maintain their mechanical properties. The polymermay contain one or more types of plasticizing groups in the polymerchains.

Example synthesis processes are shown below. In some embodiments, AtomTransfer Radical Polymerization (ATRP) is employed to form the desiredpolymers:

In a suitable organic solvent, solution of the mixture of end-caped PEG,carbon-carbon double bond substituted monomers with plasticizing groups,and carbon-carbon double bond substituted monomers with crosslinkinggroups are bubbled with nitrogen for 15 minutes. Cu(I) salt andPMDETA(N,N,N′,N″,N″-Pentamethyldiethylenetriamine) are then added. Thissolution before polymerization is referred to as electrolyte precursorsolution. The reaction is protected with nitrogen and heated to 50°C.-130° C. After a 1 hour to 48 hour reaction, the reaction mixtureappears sticky. An organic phase is filtered with celite and then thesolvent is removed by a rotary evaporator to obtain the product (polymerelectrolyte solution). The yield is 60-95%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, esterification is employed to form the desiredpolymers:

In a suitable organic solvent, solution of alcohol is added with acidchloride or active eater at −10° C. to 10° C. Base is added slowly intothe mixture and the mixture is heated to 50° C. to 130° C. for thereaction. After reacting for 1 hour to 48 hours, water is added into themixture. The organic phase is distilled to remove solvent and obtain thepolymers. The yield is 60-95%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, random copolymer is employed to form the desiredpolymers:

In reaction (1), in a suitable organic solvent, solution of amine isadded with acid chloride at −10° C. to 10° C. Base is added slowly intothe mixture, and the mixture is heated to 50° C. to 130° C. for thereaction. After reacting for 1 hour to 48 hours, water is added into themixture. The organic phase is distilled to remove solvent and obtain thepolymers. The yield is 60-95%.

In reaction (2), alkyne and azide monomer are added to a suitableorganic solvent under nitrogen. Copper(I) salt is then added ascatalyst. The solution is reacted at 10° C. to 130° C. for 1 hour to 48hours. Water is added into the mixture. The organic phase is distilledto remove solvent and obtain the polymers. The yield is 60-95%.

For reaction (3), in a suitable organic solvent, solution of the alcoholmonomer is added with triphosgene and base orN,N′-Carbonyldiimidazole(CDI) at −10° C. to 10° C. The mixture isstirred at 10° C. to 130° C. for 1 hour to 48 hours. Water is added intothe mixture. The organic phase is distilled to remove solvent and obtainthe polymers. The yield is 60-95%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, the solid electrolyte layer 108 may include ionconducting polymers chemically linked with plasticizing linear polymersthat have a glass transition temperature less than −20° C. Examplelinear polymers include, but are not limited to, polyethylene,polybutylene, polyisodibutylene, siloxane, etc. By linking theseplasticizing linear polymers with ion conducting polymers, the ionconductivity and transparency of the polymers can also be enhanced.

Example polymer electrolytes may include, but be not limited to:

wherein each of x, y, and z is an integer greater than 0, and

SP means soft polymers with low glass transition temperature (<−20° C.).The connection between different parts of main chain and the connectionbetween main chain and CL can be any type of one or several organicbonds.

Cross-linking (CL) groups may include any function chemicals which canconnect with two or more monomers. Example CL groups may include, butare not limited to:

In some embodiments, suitable polymers for ECD electrolytes may be formwith polyethylene, PEO, and cross-linking groups. Example reactionsinclude, but are not limited to:

In the above reactions, in a suitable organic solvent, a solution ofalcohol monomers and functionalized polyethylene is added withtriphosgene and base or N,N′-Carbonyldiimidazole(CDI) at −10° C. to 10°C. The mixture is stirred at 10° C. to 130° C. for 1 hour to 48 hours.Water is added into the mixture. The organic phase is distilled toremove solvent and obtain the polymers. The yield is 60-95%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, suitable polymers for ECD electrolytes may be formwith polyisobutylene, PEO, and cross-linking groups. Example reactionsinclude, but are not limited to:

In the above reactions, in a suitable organic solvent, a solution ofalcohol monomers and functionalized polyisobutylene is added withtriphosgene and base or N,N′-Carbonyldiimidazole(CDI) at −10° C. to 10°C. The mixture is stirred at 10° C. to 130° C. for 1 hour to 48 hours.Water is then added into the mixture. The organic phase is distilled toremove solvent and obtain the polymers. The yield is 60-95%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, suitable polymers for ECD electrolytes may beformed with siloxane, PEO, and cross-linking groups. Example reactionsinclude, but are not limited to:

In the above reactions, in a suitable organic solvent, a solution of allstarting materials and siloxane is added with triphosgene and base orN,N′-Carbonyldiimidazole(CDI) or catalyst at −10° C. to 10° C. Themixture is stirred at 10° C. to 130° C. for 1 hour to 48 hours. Water isthen added into the mixture. The organic phase is distilled to removesolvent and obtain the polymers. The yield is 60-95%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, a suitable polymer for ECD electrolytes may beformed as follows:

In this reaction, 3 g (10 mmol) of Polyethylene glycol (Mn˜300), 3.0 g(1 mmol) of Poly(dimethylsiloxane) bis(3-aminopropyl)terminated(Mn˜3000), triethylenetetramine 0.015 g (0.1 mmol) are addedto 100 mL dichloromethane(DCM). The solution is cooled to 0° C. beforetriphosgene 1.13 g (3.8 mmol) is added into the solution slowly.Triethylamine 2.5 g (24.7 mmol) is added dropwisely. After stirring at0° C. for 2 hours, the solution is warmed back to room temperature andstirred for 18 hours. DI water 100 ml is added into the mixture to washthe organic solution. The organic phase is collected and dried withMgSO₄ and then distilled under vacuum to remove the solvent and obtainthe product (polymer A). The yield is 80-100%.

In some embodiments, a suitable polymer for ECD electrolytes may beformed as follows:

In this reaction, 6 g (1 mmol) of Polyethylene glycol (Mn-6000), 3.0 g(1 mmol) of Poly(dimethylsiloxane) bis(3-aminopropyl)terminated(Mn-3000), triethylenetetramine 0.015 g (0.1 mmol) are addedto 100 mL dichloromethane(DCM). The solution is cooled to 0° C. beforetriphosgene 0.21 g (0.71 mmol) is added into the solution slowly.Triethylamine 0.47 g (4.6 mmol) is added dropwisely. After stirring at0° C. for 2 hours, the solution is warmed back to room temperature andstirred for 18 hours. DI water 100 ml is added into the mixture to washthe organic solution. The organic phase is collected and dried withMgSO₄ and then distilled under vacuum to remove the solvent and obtainthe product (polymer B). The yield is 80-100%.

In some embodiments, a suitable polymer for ECD electrolytes may beformed as follows:

In this reaction, 6 g (1 mmol) of Polyethylene glycol (Mn-6000), 3.0 g(1 mmol) of Poly(dimethylsiloxane) bis(3-aminopropyl)terminated(Mn-3000) are added to 100 mL toluene. The solution is cooledto 0° C. before 0.324 g (2 mmol) N,N′-Carbonyldiimidazole(CDI) is addedinto the solution slowly. After stirring at 0° C. for 2 hours, thesolution is heated to 60° C. and stirred for 18 hours. DI water 100 mlis added into the mixture to wash the organic solution. The organicphase is collected and dried with MgSO₄ and then distilled under vacuumto remove the solvent and obtain the product (polymer C). The yield is80-100%.

In some embodiments, a suitable polymer for ECD electrolytes may beformed as follows:

In this reaction, 6 g (1 mmol) of Polyethylene glycol (Mn-6000), 0.8 g(1 mmol) of Poly(dimethylsiloxane) diglycidyl ether terminated andtriethylamine 0.1 g (1 mmol) are added to 100 mL toluene. The solutionis heated to 110° C. for 24 hours. DI water 100 ml is added into themixture to wash the organic solution. The organic phase is collected anddried with MgSO₄ and then distilled under vacuum to remove the solventand obtain the product (polymer D). The yield is 80-100%.

In some embodiments, the solid electrolyte layer 108 may include ionconducting polymers chemically linked with plasticizing polymer blocksthat have plasticizing groups as side chains.

Example polymer electrolytes may include, but are not limited to:

wherein each of x, y, and z is an integer greater than 0, and

The connections between different parts of main chain, the connectionbetween main chain SP and PR, the connection between main chain and CLcan be any type of one or several organic bonds. SP are soft polymerswith low glass transition temperature (<−20° C.).

Example PR groups may include, but be not limited to:

Example CL groups may include, but be not limited to:

In some embodiments, suitable polymers for ECD electrolytes may be formwith plasticizing groups on siloxane polymers, PEO, and cross-linkinggroups. Example reactions include, but are not limited to:

In the above reactions, in a suitable organic solvent, a solution ofalcohol monomers and siloxane is added with triphosgene and base orN,N′-Carbonyldiimidazole(CDI) at −10 to 10° C. The mixture is stirred at10° C. to 130° C. for 1 hour to 48 hours. Water is then added into themixture. The organic phase is distilled to remove solvent and obtain thepolymers. The yield is 60-95%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, the solid electrolyte layer 108 may include brushcopolymers having a main chain of soft polymers and side chains ofion-conducting species and one or more non-miscible groups. Differentfrom linear type polymers, brush-type polymers are very hard to formdense packing because of the bulky sidechains. Therefore, new designs ofbrush-type polymers are proposed to avoid crystalline regions and formamorphous structure to achieve fully transparent solid electrolytes.

In some embodiments, to ensure the amorphous structures for brush-typepolymers, the polymer main chains are consisted of relatively softpolymer chains that can freely rotate. Examples of soft polymer chainsinclude siloxane chains, ethylene chains, acrylate chains, methylacrylate chains, and combinations of two or more types of the abovematerials. In some embodiments, in addition to ion-conducting species,one or more non-miscible groups can be additionally introduced into thepolymer side chains to disrupt the packing of the polymer chains. Thenon-miscible groups may be, for example, alkyl chains, aromatic groups,or any groups that are not miscible with the ion conducting groups. Ifthe brush polymer is in a liquid state or has a low mechanical modulus,cross-linking groups can be added to ensure the solid state or enhancethe mechanical modulus.

Example brush-type polymers having differing side chains to disturb thepacking of polymer include, but are not limited to:

wherein each of x, y, and z is an integer greater than 0, and the mainchain include, but is not limited to:

NM means non-miscible groups having structures including alkyl chains,aromatic groups, combination of alkyl and aromatic groups or any groupsthat are not miscible with the ion conducting groups.

IC means ionic conductivity groups that may include, but are not limitedto:

CL means Cross-linking groups including any function chemicals which canconnect two or more monomers. Example CL groups may include, but be notlimited to:

In some embodiments, the connection between different parts of mainchain, the connection between main chain and IC, the connection betweenmain chain and NM, the connection between main chain and CL can be anytype of one or several organic bonds.

Two methods may be employed to form the above polymers for ECDelectrolytes. The first method includes forming the main chain polymerfirst and then grafting the different side chains onto the main chain toobtain the desired polymers. The second method includes forming monomersor oligomers with different types of side chains and then polymerizingto obtain the desired polymers.

In an example first method, siloxane is employed as the main chain. Forexample, a desired polymer may be formed by the reactions including, butare not limited to:

In the above reactions, in a suitable organic solvent, solution ofpolymethylhydrosiloxane, vinyl substituted non-miscible groups, vinylsubstituted ionic conductive group, and vinyl substituted crosslinkgroups is bubbled with nitrogen for about 15 min. Pt as a catalyst isthen added. The reaction is protected with nitrogen and heated to 40° C.to 110° C. After 1 hour to 24 hours, the reaction mixture appearssticky. The solvent of the mixture is removed with a rotary evaporatorto obtain the product. The yield of the process is 60-97%.

In some embodiment, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

Another example polymer for ECD electrolytes may be formed according tothe following reaction:

In this reaction, 2.3 g (˜1 mmol) Poly(methylhydrosiloxane)(Mn=2100-2400), 0.56 g (5 mmol) 1-Octene, 7.14 g (35 mmol)Allyloxy(triethylene oxide) methyl ether are added to 100 ml toluene.The solution is bubbled with nitrogen for about 15 min followed byadding Karstedt's catalyst 0.4 g (0.4 mmol) under nitrogen. The reactionis protected with nitrogen and heated to 50° C. After 24 hours, thereaction mixture appears sticky. The solvent of the mixture is removedwith a rotary evaporator to obtain the product (polymer A). The yield ofthe process is 80-100%.

Yet another example polymer for ECD electrolytes may be formed accordingto the following reaction:

In this reaction, 2.3 g (−1 mmol) Poly(methylhydrosiloxane)(Mn=2100-2400), 0.56 g (5 mmol) 1-Octene, 6.73 g (33 mmol)Allyloxy(triethylene oxide) methyl ether, 0.22 g (2 mmol) 1,7-Octadieneare added to 100 ml toluene. The solution is bubbled with nitrogen forabout 15 min followed by adding Karstedt's catalyst 0.4 g (0.4 mmol)therein under nitrogen. The reaction is protected with nitrogen andheated to 50° C. After 24 hours, the reaction mixture appears sticky.The solvent of the mixture is removed with a rotary evaporator to obtainthe product (polymer B). The yield of the process is 80-100%.

Another example polymer for ECD electrolytes may be formed according tothe following reaction:

In this reaction, 2.3 g (˜1 mmol) Poly(methylhydrosiloxane)(Mn=2100-2400), 0.52 g (5 mmol) Styrene, 6.73 g (33 mmol)Allyloxy(triethylene oxide) methyl ether, 0.22 g (2 mmol) 1,7-Octadieneare added to 100 ml toluene. The solution is bubbled with nitrogen forabout 15 min. before Karstedt's catalyst 0.4 g (0.4 mmol) is addedtherein under nitrogen. The reaction is protected with nitrogen andheated to 50° C. After 24 hours, the reaction mixture appears sticky.The solvent of the mixture is removed with a rotary evaporator to obtainthe product (polymer C). The yield of the process is 80-100%.

In another example first method, 1,2-polybutadiene is employed as themain chain. For example, a desired polymer may be formed by thereactions including, but not limited to:

Condition 1: Polymerization by heating. 1,2-polybutadiene, with orwithout a radical initiator, thiol substituted non-miscible groups, athiol substituted ionic conductive group, and a thiol substitutedcrosslink group are mixed in a suitable organic solvent solution or ano-solvent condition. The mixture is heated at 40° C. to 110° C. for 10minutes to 24 hours, resulting in a sticky solution or solid. Thesynthesized sticky solution or solid can be used the target polymerelectrolyte, which can be coated on a working electrode or a counterelectrode to form a solid electrolyte film.

In some embodiments, the mixture of all the starting materials (called“precursors” for the electrolyte or electrolyte precursor solution)before polymerization can also be used for device fabrication usingin-situ polymerization under heating.

Condition 2: Polymerization by UV light. 1,2-Polybutadiene, with orwithout a radical initiator, thiol substitute non-miscible groups, athiol substituted ionic conductive group, and a thiol substitutedcrosslink group are mixed in a suitable organic solvent solution or ano-solvent condition. The mixture is exposed to UV light for 2 minutesto 150 minutes, resulting in a sticky solution or solid. The synthesizedsticky solution or solid can be used as the target polymer electrolyte,which can be coated on a working electrode or a counter electrode toform a solid electrolyte film.

In some embodiments, the mixture of all the starting materials (called“precursors” for the electrolyte or electrolyte precursor solution)before polymerization can also be directly used for device fabricationusing in-situ polymerization under UV light.

Example radical initiators include, but are not limited to: tert-Amylperoxybenzoate, 4,4-Azobis(4-cyanovaleric acid),1,1′-Azobis(cyclohexanecarbonitrile), 2,2′-Azobisisobutyronitrile,Benzoyl peroxide2, 2,2-Bis(tert-butylperoxy)butane,1,1-Bis(tert-butylperoxy)cyclohexane,2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane,2,5-Bis(tert-Butylperoxy)-2,5-dimethyl-3-hexyne,Bis(1-(tert-butylperoxy)-1-methylethyl)benzene,1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclo-hexane, tert-Butylhydroperoxide, tert-Butyl peracetate, tert-Butyl peroxide, tert-Butylperoxybenzoate, tert-Butylperoxy isopropyl carbonate, Cumenehydroperoxide, Cyclohexanone peroxide, Dicumyl peroxide, Lauroylperoxide, 2,4-Pentanedione peroxide, Peracetic acid, and Potassiumpersulfate.

In an example second method, monomers with different type of side chainsare formed and then polymerized to obtain the desired polymer. Forexample, a desired polymer may be formed by the reactions including:

Condition 1: Polymerization by heating. a monomer with non-misciblegroups, a monomer with ionic conductive group, and a monomer withcrosslinking group, with or without a radical initiator are mixed in asuitable organic solvent solution or a no-solvent condition. The mixtureis heated to 40° C. to 110° C. for 10 minutes to 24 hours, resulting ina sticky solution or solid. The synthesized sticky solution or solid canbe used as the target polymer electrolyte, which can be coated on aworking electrode or a counter electrode to form a solid electrolytefilm.

In some embodiments, the mixture of all the starting materials (called“precursors” for the electrolyte or electrolyte precursor solution)before polymerization can also be directly used for device fabricationusing in-situ polymerization under heating.

Condition 2: Polymerization by UV light. a monomer with non-misciblegroups, a monomer with ionic conductive group, and a monomer withcrosslinking group, with or without a radical initiator are mixed in asuitable organic solvent solution or a no-solution condition. Themixture is exposed to UV light for 2 minutes to 150 minutes, resultingin a sticky solution or solid. The synthesized sticky solution or solidcan be used as the target polymer electrolyte, which can be coated on aworking electrode or a counter electrode to form a solid electrolytefilm.

In some embodiments, the mixture of all the starting materials (called“precursors” for the electrolyte or electrolyte precursor solution)before polymerization can also be used for device fabrication usingin-situ polymerization under UV light.

Example radical initiators include, but are not limited to: tert-Amylperoxybenzoate, 4,4-Azobis(4-cyanovaleric acid),1,1′-Azobis(cyclohexanecarbonitrile), 2,2′-Azobisisobutyro-nitrile,Benzoyl peroxide2, 2,2-Bis(tert-butylperoxy)butane,1,1-Bis(tert-butylperoxy)cyclo-hexane,2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane,2,5-Bis(tert-Butylperoxy)-2,5-dimethyl-3-hexyne,Bis(1-(tert-butylperoxy)-1-methyl-ethyl)benzene,1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-Butylhydroperoxide, tert-Butyl peracetate, tert-Butyl peroxide, tert-Butylperoxybenzoate, tert-Butylperoxy isopropyl carbonate, Cumenehydroperoxide, Cyclohexanone peroxide, Dicumyl peroxide, Lauroylperoxide, 2,4-Pentanedione peroxide, Peracetic acid, and Potassiumpersulfate.

In some embodiments, a desired polymer may be formed by the reactionsincluding, but not limited to:

In these reactions, in a suitable organic solvent, a solution ofnorbornene monomer with non-miscible groups, a norbornene monomer withionic conductive group, and a norbornene monomer with crosslinkinggroups is bubbled with nitrogen for 15 min. Grubbs catalyst is thenadded therein. The reaction is protected with nitrogen and heated to 40°C. to 110° C. After 10 minutes to 24 hours, the reaction mixture appearssticky. The solvent of the mixture is removed with a rotary evaporatorto obtain the product. The yield of the process is 60-97%.

In some embodiments, the mixture of all the starting materials (calledprecursors for electrolyte or electrolyte precursor solution) beforeheating can also be used for device fabrication using in-situpolymerization under heating.

In some embodiments, before being processed into a solid electrolytethin film for an electrochromic device, any one or more of the abovepolymer electrolytes or electrolyte precursors (e.g., the mixture of allof the monomers or oligomers with or without one or more radicalinitiators, with or without catalyst before polymerization) may beblended with one or more types of organic or inorganic salts. Exampleinorganic salts include Li+, Na+, K+, Mg2+, Ca2+, Al3+ based salts, andothers now known or later developed. Example organic salts include ionicliquids such as EMITFSI, EMIOTF, and others now known or laterdeveloped.

In some embodiments, before blending with any one or more of the examplesalts, any one or more of the polymer electrolytes disclosed herein maybe dissolved in one or more appropriate solvents. The solvent(s) canhelp blend the polymers and salt(s) well, and can be removed byevaporation after being coated into films. The polymer electrolytesolution can be coated into films using any one of a variety ofconventional solution-compatible coating strategies, including, but notlimited to, spray coating, spin coating, slot-die coating, slit coating,roll-to-roll coating, transfer coating, and wire bar coating.

Reference is now made to FIG. 2. FIG. 2 is a flow chart illustrating amethod 200 for forming an electrochromic device, according to oneexample embodiment. At 202, a first flexible substrate is coated with afirst transparent electrode. The first transparent electrode mayinclude, but is not limited to, indium-tin oxide (ITO), aluminum zincoxide (AZO), fluorine doped tin oxide (FTO), silver nanowires, graphene,carbon nanotube, metal mesh based transparent conductive electrodes, orsilver-nanoparticle ink. The first transparent electrode may becoated/deposited using physical or chemical vapor deposition methods,such as sputtering. At 204, on the first flexible substrate, anelectrochromic layer is coated on the first transparent electrode. At206, a second flexible substrate is coated with a second transparentelectrode. The second transparent electrode may include, but is notlimited to, indium-tin oxide (ITO), aluminum zinc oxide (AZO), fluorinedoped tin oxide (FTO), silver nanowires, graphene, carbon nanotube,metal mesh based transparent conductive electrodes, orsilver-nanoparticle ink. The second transparent electrode may becoated/deposited using physical or chemical vapor deposition methods,such as sputtering. At 208, on the second flexible substrate, an ionstorage layer is coated on the second transparent electrode.

At 210, a polymer electrolyte solution or an electrolyte precursorsolution is provided onto a surface of the electrochromic layer, or ontoa surface of the ion storage layer, or onto a surface of theelectrochromic layer and a surface of the ion storage layer, or onto thegap between a surface of the electrochromic layer and a surface of theion storage layer. At 212, the first flexible substrate is laminatedwith the second flexible substrate such that an area of one of thesubstrates is not covered by another one of the substrates and such thatthe electrolyte solution is interposed between the electrochromic layerand the ion storage layer.

For example, one or both of the first flexible substrate (WE) and thesecond flexible substrate (CE) as prepared by the above operationsis/are laid flat on a flat surface such as a marble plate, glass or thelike. The polymer electrolyte solution or electrolyte monomer/oligomersolution (the precursor for a solid electrolyte) is applied to the firstflexible substrate and/or the second flexible substrate by any one of avariety of solution-compatible coating strategies, including spraycoating, spin coating, slot-die coating, slit coating, roll-to-rollcoating, micro concave coating, screen printing, transfer coating, wirebar coating, etc. After the electrolyte solution is uniformly spread onone or both of the substrates, the substrates are laminated with eachother. Suitable film lamination methods that may be used include, butare not limited to, cross cover, misalignment cover, and complete cover.FIGS. 3A and 3B illustrate two lamination configurations in which anarea of one of the substrates is not covered by another one of thesubstrates.

In some embodiments, after the polymer electrolyte solution is uniformlyspread on one or both of the substrates, part of the solvent of thepolymer electrolyte solution is either dried in a room temperature or inan oven at a temperature ranging from 60-140° C. with or without vacuum.Then, the substrates are laminated with each other. Suitable filmlamination methods that may be used include, but are not limited to,cross cover, misalignment cover, and complete cover.

After the lamination, a roller press machine, a flat plate pressingdevice, a vacuum pressing device, or other apparatus now known or laterdeveloped may be used for defoaming the precursor. For example, and morespecifically, the multilayer thin film assembly consisting of the WE,the CE, and the precursor therebetween may be placed in a flat platepressing apparatus and pressed at room (e.g., 1 atmosphere of pressure)temperature or a pressure of 30 MP-500 MP under heating (e.g., higherthan 90° C.) for a predetermined time, such as between 1 min and 30 min.The pressing process may be terminated after the bubbles in theelectrolyte layer are removed. Alternatively, the multilayer thin filmassembly may be placed in a rolling press machine and defoamed, forexample, at a speed of 0.5 m/s to 30 m/s at room temperature or underheating (e.g., higher than 90° C.) until the bubbles are removed fromthe electrolyte layer.

In some embodiments, the polymer electrolyte solution or electrolyteprecursor may be dripped, for example, by a dispenser, evenly betweenthe CE and the WE. The WE and CE are pressed together by a roller press,with the electrolyte precursor interposed therebetween. In someembodiments, the pressure of the roller press is in the range of 1MP-200 MP, and speed can range, for example, from about 0.1 m/s to about30 m/s. The speed of precursor drip can be estimated, for example, usingX*Y*Z ml/s, wherein X (cm) is the thickness of electrolyte, Y (cm/s) isthe speed of roller press, Z (cm) is the width of coincident part of WEand CE. This technique can be applied in a cost-effective, large-scaleon-line assembling of the ECDs.

At 214, the electrolyte solution is cured to form the electrochromicdevice. In some embodiments, the electrolyte solution may be cured by athermal process. For example, the electrolyte solution may be cured at80-120° C. at a pressure of 30 MP to 500 MP for 1 to 30 min. Forexample, the multilayer thin film assembly may be placed in an oven withuniform heat radiation and baked at a temperature of 90° C. for a timebetween 1 min and 30 min to form a fully crosslinked solid-stateelectrolyte thin film, that further bond the WE and CE thin filmstogether.

In some embodiments, the laminated device with polymer electrolytesolution interposed between two electrolyte was dried in an oven at atemperature ranging from 60-140° C. with or without vacuum to form asolid-state electrolyte thin film, that further bond the WE and CE thinfilms together.

In some embodiments, the electrolyte solution may be cured by UVirradiation. In some embodiments, the electrolyte solution is cured togenerate an electrolyte layer having less than 20 wt % of neutral smallorganic molecules having a molecular weight of 3000 or less. In someembodiments, the electrolyte solution is cured to generate anelectrolyte layer having less than 3 wt % of neutral small organicmolecules having a molecular weight of 3000 or less. When too manyneutral small organic molecules are present in the electrolyte layer,they may inhibit the ion conductivities between the ion storage layerand the electrochromic layer. In some embodiments, the electrolytesolution may be cured to generate an electrolyte layer free of neutralsmall organic molecules that can be detected or measured by availableinstruments.

In some embodiments, the multilayer thin film assembly may be placed inan oven with uniform heat radiation and baked at a temperature of 90° C.for a time between 1 min and 30 min to form a fully crosslinkedsolid-state electrolyte thin film, that further bond the WE and CEtogether.

In some embodiments, the method 200 further includes 216 in whichmaterials on the first transparent electrode or the second transparentelectrode at the area of one of the substrates not covered by anotherone of the substrates is removed. This operation removes the material(s)above the transparent electrode and exposes the surface of thetransparent electrode. Techniques to remove the electrochromic layer,the ion storage layer, and the ion transfer (electrolyte) layer on thesurface of the substrate(s) include, but are not limited to, wiping,laser etching, and plasma etching. When wiping with a dust-free paper, adust-free cloth, or the like, an appropriate solvent may be employedthat can dissolve the materials from those layers. For example, thewiping solvent may include, but not be limited to, acetone, ethanol,o-xylene, among others known in the art. Before wiping, a mold of silicagel or other material with the same shape may be used as a protector toavoid film peeling and contamination of the area. When laser etching isused, the apparatus's parameters can be determined according to thethickness and material characteristics of the WE, CE, and ion transportlayer. For example, the laser etching may be conducted at a speed of 10mm/s-600 mm/s, using an energy of 10 w-200 w and a frequency at 10Hz-20000 Hz.

At 218, a circuit is attached to the area. For example, a circuit tocontrol the electrochromic device is connected to the exposedtransparent electrode. The circuit can be attached to the area, forexample, by adhering a double-sided conductive tape or dispensing theconductive paste/ink to the area to form the conductive wires with acertain width in the exposed conducting areas. A flexible printedcircuit board, silver paste, or copper wire can be adhered onto thecircuit and extended to make connection with a power source.

The all solid-state thin film electrochromic device formed using theabove operations can then be encapsulated into various products forvarious applications, such as in automobiles, airplanes, buildings,sunglasses, medical treatment, and education, among many others.

Embodiment 1

1. Preparation of WE Thin Film

800 mg of the poly(ethylhexanepropylenedioxythiophene) is dissolved in10 ml of o-xylene, magnetically stirred for ten hours to form asolution. The solution is uniformly applied to the surface of thenano-silver transparent conductive film (a substrate coated with anano-silver conductive layer) by a sheet slit coating apparatus. Thecoated electrochromic layer film is baked at a high temperature of 120°C. for 30 min to form a film with a good adhesion on the surface of theflexible conductive substrate to obtain a WE. Thereafter, theas-fabricated electrochromic layer film is cut into a shape 402 as shownin FIG. 4 by a die cutting machine.

2. Preparation of Ion Storage Layer Film (CE)

A magnetron sputtering technique is used to deposit a tungsten trioxidefilm with a thickness of several tens of micrometers on the surface ofthe nano-silver transparent flexible conductive film at room temperatureto obtain an ion storage layer film. The ion storage layer film is thencut into the same shape (404) as the electrochromic layer film by a diecutter as shown in FIG. 4.

3. Preparation of Ion Transfer Layer

A brush-type polymer is employed as the ion transfer layer(electrolyte). The polymer is mixed with a lithium salt and anultraviolet curing initiator in a mass ratio of 45/45/10. After magneticstirring for 30 minutes, ultrasonic vibration is used to defoam themixture for 30 minutes to obtain a precursor solution that is ready touse. The precursor 502 is dispensed on the edge of the electrochromiclayer 504 and is uniformly distributed to the surface of the WE 506 by awire bar coater 508, as shown in FIG. 5.

4. Fitting and Curing

The ion storage layer is overlaid on the electrolyte-coatedelectrochromic layer in a staggered manner, as shown in FIG. 6 with theWE and CE facing each other. The laminated composite film is then fedinto a roller press to remove air bubbles in the composite film layer.After defoaming, the laminated ECDs is placed under UV light, and theelectrolyte precursor is thereby thoroughly crosslinked to form a solidcomposite and to bond WE and CE together to form an ECD.

5. Exposure of the Conductive Areas and Circuit Layout

The electrolyte and WE left on the reserved circuit area (in a stripshape) are wiped off with acetone. The ion storage layer is etched awaywith a laser to expose the conductive layer. A copper conductive tape702 is adhered on the exposed area of the conductive layer and extendedout to be the positive and negative electrodes, wherein the leadconnected to the WE is a positive electrode, and the lead connected tothe CE is a negative electrode. The circuit layout and wiring are shownin FIG. 7.

Embodiment 2

1. Preparation of Electrochromic Layer Thin Film (WE)

800 mg of ECP (a copolymer of the 2,5-dibromo- and2,5-tributylstannyl-2-ethyl-hexyloxy-substitutedethylhexane-3,4-propylenedioxythiophene (ProDOT-(CH₂OEtHx)₂) and4,7-dibromo-2,1,3-benzothiadiazole (BTD)) is dissolved in 10 ml ofo-xylene, magnetically stirred for ten hours to form a solution. Thesolution is uniformly applied to the surface of the ITO transparentconductive film by spin-coating. Then, the coated electrochromic layerfilm is baked at a temperature of 120° C. for 30 min to form a film thatadheres well to the surface of the flexible conductive film to obtain anelectrochromic layer film. Thereafter, the electrochromic layer film iscut into a desired shape by a die cutting machine.

2. Preparation of Ion Storage Layer Film (CE)

An ink of Nb₂O₅, with or without doping of TiO₂, is coated via theslot-die coating with a thickness of several tens of nanometers on thesurface of an ITO transparent flexible conductive film at roomtemperature to obtain an ion storage layer film.

3. Preparation of Ion Transfer Layer

A brush-type polymer is employed as the ion transfer layer(electrolyte). The polymer is mixed with a lithium salt and a thermalcuring initiator in a mass ratio of 50/45/5. After magnetic stirring for10 min, ultrasonic vibration is used to defoam the mixture for 10 min toobtain a precursor solution that is ready to use. The precursor isuniformly applied to the surface of the electrochromic layer by screenprinting.

4. Fitting and Curing

The ion storage layer is overlaid on the electrolyte-coatedelectrochromic layer in a staggered manner. The laminated composite filmis then flattened by a vacuum laminating machine and defoamed at a highpressure to remove bubbles in the composite film layer, and then thecomposite film is cured at a high temperature of 100° C. for 10 min toform a solid composite and to bond WE and CE together to form an ECD.

5. Exposure of the Conductive Areas and Circuit Layout

The electrolyte and WE left on the reserved circuit area (in a stripshape) are wiped off with acetone. The ion storage layer is etched awaywith a laser to expose the conductive layer. A silver wire or a silverpaste cloth is used to form the circuit on the exposed area of theconductive layer, and the positive and negative electrodes are wired outby fixing the FPC using silver glue, wherein the lead connected to theWE is a positive electrode, and the lead connected to the CE is anegative electrode.

Embodiment 3

1. Preparation of Electrochromic Layer Thin Film (WE)

Thin film preparation steps are same as described in the embodiment 1,above. Other than that, the WE is cut into a square shape with a size of2 cm×2 cm by a die cutting machine.

2. Preparation of Ion Storage Layer Film (CE)

Thin film preparation steps are same as described in embodiment 2,above. Other than that, the CE is cut into a square shape with a size of2 cm×2 cm by a die cutting machine.

3. Preparation of Ion Transfer Layer

Same as described in embodiment 1, above.

4. Fitting and Curing

The ion storage layer is overlaid on the electrolyte-coatedelectrochromic layer in a staggered manner. The laminated thin film isthen flattened by a vacuum laminating machine and defoamed at a highpressure to remove bubbles in the composite film layer, and then theelectrolyte precursor is thoroughly crosslinked via UV irradiation toform a solid composite and to bond the WE and the CE together to form anECD.

5. Exposure of the Conductive Areas and Circuit Layout

The electrolyte and WE left on the reserved circuit area (in a stripshape) are wiped off with acetone. The ion storage layer is etched awaywith a laser to expose the conductive layer. A copper tape is used toform the circuit on the exposed area of the conductive layer, and thepositive and negative electrodes are wired out by capper tapes, whereinthe lead connected to the WE is a positive electrode, and the leadconnected to the CE is a negative electrode.

Embodiment 4

1. Preparation of Electrochromic Layer Thin Film (WE)

1000 mg of the poly(ethylhexane propylenedioxythiophene) is dissolved in10 ml of o-xylene, magnetically stirred for ten hours, and the solutionis uniformly applied to the surface of the nano-silver transparentconductive film by a sheet slit coating apparatus. The coatedelectrochromic layer film is baked at a high temperature of 120° C. for30 min to form a film with good adhesion on the surface of the flexibleconductive substrate to obtain a WE (802). Thereafter, the WE 802 is cutinto a shape as shown in FIG. 8A by a die cutting machine.

2. Preparation of Ion Storage Layer Film (CE)

Prussian blue functionalized with ligands is suspended in alcohol andcoated on the surface of the transparent FTO flexible conductive film bya slit coating technique to obtain an ion storage layer film. Aftercoating, the film is baked at 100° C. for 20 min to obtain a CE (804)(FIG. 8A). The ion storage layer film is then cut into the same shape asthe electrochromic layer film by a die cutting machine.

3. Preparation of Ion Transfer Layer

Same as described in embodiment 1, above.

4. Fitting and Curing

The ion storage layer is overlaid on the electrolyte-coatedelectrochromic layer in a staggered manner, as shown in FIG. 8B. Thelaminated composite film is fed into a roller press to remove airbubbles in the composite film layer. After defoaming from the rollpress, the composite film electrochromic layer is cured under UVirradiation to obtain the all solid state ECD.

5. Exposure of the Conductive Areas and Circuit Layout

The electrolyte, WE 802 and CE 804 left on the reserved circuit area arewiped off with acetone. A silver wire or a silver paste cloth is used toform the circuit 806 on the exposed area of the conductive layer. Theconductive cloth is placed on the exposed area of the conductive layerto directly wire out the positive and negative electrodes, wherein thelead-out end of the electrochromic layer is a positive electrode, andthe lead portion of the ion storage layer is a negative electrode. Thecircuit layout is shown in FIG. 8C.

Embodiment 5

1. Preparation of Electrochromic Layer Thin Film (WE)

Thin film preparation steps are the same as described in embodiment 1,above. Other than that, the WE is cut into a rectangular shape with asize of 4 cm×20 cm by a die cutting machine.

2. Preparation of Ion Storage Layer Film (CE)

Thin film preparation steps are the same as described in embodiment 2,above. Other than that, CE is cut into a rectangular shape with a sizeof 4 cm×20 cm by a die cutting machine.

3. Preparation of Ion Transfer Layer

Same as described in embodiment 1, above.

4. Fitting and Curing

Same as described in embodiment 1, above. Other than that, the all-solidstate ECD is a rectangular shape with a size of 4 cm×20 cm by a diecutting machine.

Embodiment 6

1. Preparation of Electrochromic Layer Thin Film (WE)

600 g of ECP (a copolymer of the 2,5-dibromo- and2,5-tributylstannyl-2-ethyl-hexyloxy-substitutedethylhexane-3,4-propylenedioxythiophene (ProDOT-(CH₂OEtHx)₂) and4,7-dibromo-2,1,3-benzothiadiazole (BTD)) is dissolved in 10 L ofo-xylene and magnetically stirred for ten hours to form a solution. Thesolution is uniformly applied to the surface of full roll of PETsubstrate with ITO transparent conductive film by roll to roll coating.The width of the PET substrate is 50 cm. Then, the coated electrochromiclayer film was baked at a high temperature of 140° C. for 3 min. The WEthin film is then winded into a roll.

2. Preparation of Ion Storage Layer Film (CE)

Prussian blue functionalized with ligands is suspended in alcohol andcoated on the surface of a full roll of PET substrate with ITOtransparent conductive film by roll to roll coating. The width of thePET substrate is 50 cm. After coating, the film is baked at 120° C. for2 min. After that, a roll of CE thin film is obtained by winding.

3. Preparation of Ion Transfer Layer

Same as described in embodiment 1, above.

4. Fitting and Curing

Reference is made to FIG. 9. The CE film 902 and the WE film 904 arepressed together in a roller press 906. And those two films arecompletely coincident. The speed of roller press 906 is 5 m/s. The rateof the precursor drip 908 is 25 ml/s. At the same time, the dispenser909 dripped the electrolyte precursor evenly in the middle of the CEfilm 902 and the WE film 904 as shown in FIG. 9. The laminated ECD isexposed to UV radiation, and the electrolyte is thereby crosslinked toform a solid composite and to bond the WE 904 and the CE 902 together.

5. Exposure of the Conductive Areas and Circuit Layout

The large size all solid-state device is cut into a desired shape bylaser semi-cutting technology. Then, the electrolyte, the CE, and the WEleft on the reserved circuit area (in a strip shape) are wiped off withacetone. A copper conductive tape is adhered on the exposed area of theconductive layer and extended out to be the positive and negativeelectrodes, wherein the lead connected to the WE is a positiveelectrode, and the lead connected to the CE is a negative electrode.

Embodiment 7

1. Preparation of Electrochromic Layer Thin Film (WE)

600 mg of ECP (a copolymer of the 2,5-dibromo- and2,5-tributylstannyl-2-ethyl-hexyloxy-substitutedethylhexane-3,4-propylenedioxythiophene (ProDOT-(CH₂OEtHx)₂) and4,7-dibromo-2,1,3-benzothiadiazole (BTD)) is dissolved in 10 ml oftoluene and magnetically stirred for ten hours to form a solution. Thesolution is uniformly applied to the surface of a flexible ITOtransparent conductive substrate with a size of 10 cm×10 cm by slot-diecoating. Then, the coated WE is baked at a high temperature of 80° C.for 30 min to form a film and to adhere well to the surface of theflexible conductive film to obtain the WE.

2. Preparation of Ion Storage Layer Film (CE)

400 mg of poly(nitronylnitroxylstyrene) is dissolved in 10 ml ofN-Methyl-2-Pyrrolidone and magnetically stirred for ten hours to form asolution. The solution is uniformly applied to the surface of a flexibleITO transparent conductive substrate with a size of 10 cm×10 cm byslot-die coating. The coated CE film is dried at a temperature of 100°C. for 30 min to form the CE.

3. Preparation of Ion Transfer Layer

Ion conducting polymers chemically linked with plasticizing linearpolymers are used in this embodiment. The polymers are mixed with alithium salt in a mass ratio of 60/40. After magnetic stirring for 30minutes, ultrasonic vibration is used to defoamed the mixture for 30minutes to get a precursor solution that is ready to use. The precursoris dripped by a dispenser evenly between the CE film and the WE film.The as-fabricated WE or and CE are pressed together in a roller presswith the electrolyte precursor disposed therebetween. The pressure ofthe roller press is 100 MP, and speed is 10 m/s. The rate of precursordrip is 10 ml/s. The composite film is cured at a high temperature of100° C. for 10 min to form a solid composite and to bond the WE and CEtogether.

4. Fitting and Curing

The electrolyte and WE left on the reserved circuit area (in a stripshape) are wiped off with acetone. The ion storage layer is etched awaywith a laser to expose the conductive layer. A copper tape is used toform the circuit on the exposed area of the conductive layer, and thepositive and negative electrodes are wired out by fixing the FPC usingsilver glue, wherein the lead connected to the WE is a positiveelectrode, and the lead connected to the CE is a negative electrode.

Due to the lack of physical support, the requirement of chambers forreceiving the electrolytes, and the delicate sealing techniques needed,liquid or gel based ECDs are not robust and cannot be easily bent. Theembodiments of this disclosure provide a solid electrolyte layer whichcompletes solid-state ECDs. The ECDs of the present disclosure can bebent and fixed into 0 degrees to 360 degrees bended shapes, with smallradii of curvature (e.g., as low as 2.5 cm), which demonstrates thecapability to be adapted to any surface having virtually any shape(s)and curvature(s). For example, as shown in FIG. 10, thin-filmall-solid-state ECDs made consistent with embodiments of the presentdisclosure are bent and fixed into certain degrees, and theirtransmittance changes have been measured in-situ when switching between−1.2 and 1.5 V. The radius of curvature of the ECD bent at 45 degree is7.8 cm in this example. The most extreme bending in this example,wherein the radius of curvature was 4.2 cm, demonstrated by thedisclosed all-solid-state ECDs was 90 degrees, which shows a greatpotential to be adapted onto most of the curved surfaces in manyapplications including sunroof, rearview mirror, building windows, andso on. In contrast, to achieve any significant degree of bending withoutcausing the issues (like the damage of WE or CE, contact of WE and CEwith one another, etc.), tremendous efforts are needed in the sealingand encapsulation of liquid or gel based ECDs known in the art. ECDs ofthe present disclosure that have all-solid electrolyte layers, however,do not require any such measures.

FIG. 11 are pictures showing ECDs in operations according to exampleembodiments. In FIG. 11(A), ECDs are in a colored/dimming state (up) anda bleached state (down) without bending. In FIG. 11(B), the ECD is inthe colored/dimming state when curved into a near semi-circle. In FIG.11(C), the ECD is in the bleached state when curved into a nearsemi-circle. In FIG. 11(D), the ECD is in the colored/dimming state whencurved into a circle. FIG. 11(E), the ECD is in the bleached state whencurved into a circle. These examples indicate that the ECDs formedaccording to the embodiments of this disclosure are very flexible andstable.

The disclosed all-solid-state ECDs demonstrate rapid switching time forcoloring and bleaching. For example, 0.1 s-1 s switching times can beachieved. A 2 cm×2 cm ECD is subjected to one second double-potentialswitching between −1.2 and 1.5 V, and the transmittance change ismeasured in-situ. As shown in FIG. 12, the ECD switched in one secondcan achieve ˜90% of the optical contrast at a complete switch, whichindicated that the tested all solid-state ECD has a fast switchingkinetic.

Due to the solid-state form of the electrolyte layer, it is possible tofabricate the electrolyte film as thin as, for example, 0.1 μm. Bymanufacturing-friendly and cost-efficient processes, including roller,plate, or vacuum press processes, among others known in the arts, it canbe easily fabricated down to, for example, 5 μm, thus the all-solidstate ECDs can be as slim as, for example, 25 μm. The thickness of eachlayer and ECDs can be further reduced. The slim design for the disclosedall-solid-state ECDs can be a great advantage to be applied for smallintegrated systems.

Due to very low viscosity of a liquid or gel electrolyte, the roller,plate, or vacuum press processes cannot be used for liquid or gelelectrolyte based ECDs. However, due to the robustness and hightemperature tolerance, the disclosed all-solid-state ECDs allowcontinuous manufacturing friendly and cost-efficient processes, such asroll-to-roll coating and roller press processes for cheap large-scaleon-line production and allow easy encapsulation into products forvarious applications.

Further, due to the use of the solid-state electrolyte, there will be nodelamination, or many side reactions occurring at the WE, CE/electrolyteinterfaces. Thus, the disclosed ECDs show a better cycling performance.Low voltage consumption of the disclosed solid-state ECDs (can be as lowas 1.5 V) is beneficial for battery powered applications.

The ECDs formed according to the above techniques can be used inanti-glare rearview mirrors for vehicles. FIG. 13A is an explosivediagram of an anti-glare rearview mirror 1300 containing an ECDaccording to one example embodiment. FIG. 13B is a schematic diagramillustrating a cross-section view of the anti-glare rearview mirror1300. FIG. 13C is another schematic diagram illustrating a cross-sectionview of the anti-glare rearview mirror 1300. The edges of the adhesivelayers can be flush with (FIG. 13B) or beyond edges of the ECD (FIG.13C). The anti-glare rearview mirror 1300 includes a mirror 1310, anadhesive layer 1320, a solid-state ECD 1330, a glass plate 1340, and asealant 1350.

The mirror 1310 has two surfaces. Normally, the surface facing to theadhesive 1320 is coated with a reflective layer, which may be made by apure metal (such as cadmium, silver, aluminum, rhodium, iridium or thelike), an alloy (such as bronze, silver alloy or the like), anon-metallic material (such as silicon dioxide, titanium dioxide withpolymer matrix or the like), a hybrid material (such as metal withnon-metal materials), or the combination thereof. In some cases, thesurface facing to the air instead of the adhesive 1320 can also becoated with a reflective layer to perform as a mirror. The thickness ofthe reflective layer ranges, for example, from 0.01 mm to 0.5 mm. Thethickness of the mirror ranges, for example, from 0.5 mm to 2.5 mm. Thereflection rate of the mirror ranges, for example, from 50% to 100%. Themirror can be flat or with a certain or varied curvature. Regarding thenon-flat mirrors, curvature radius ranges, for example, from 10 mm to1500 mm.

The adhesive 1320 is a transparent adhesive. Example transparentadhesives include optical clear adhesive (OCA) (for example resin OCA,liquid OCA or solid OCA), hot melting adhesives (including but notlimited to ethylene vinyl acetate membrane (EVA) and polyvinyl butyralmembrane (PVB)), among others now known or later developed. Examplecuring methods include moisture curing, heat curing, UV curing, amongothers now known or later developed. When it comes to optical clearadhesive, UV curing, or moisture curing is commonly performed after theadhesive is applied to the surface or encapsulated in the EC mirror.When it comes to hot melting adhesive, heat curing is commonly performedduring the incorporating process. The light transmittance of theselected adhesive may be between 80%-100%. Besides, the selectedadhesive needs to have a similar refractive index with the one from theglass, which is normally between 1.1-1.6. The thickness of the adhesiveranges, for example, from 0.05 mm to 0.5 mm.

The all solid-state thin-film electrochromic device (ECD) 1330 isconsistent with those disclosed above. The thickness of the ECD 1330ranges, for example, from 0.02 mm to 3.0 mm.

The glass plate 1340 may have a high light transmission rate between50%-100%. Typically, the surface facing the opposite of the EC mirror ismodified to eliminate the reflective rate with a reflection rate lessthan 4%. The glass can be flat or with a certain or varied curvature.Regarding the non-flat glass plates, curvature radius ranges, forexample, from 10 mm to 1500 mm.

The sealant 1350 has very good adhesion to the glass and is waterproof.Example sealant includes butyl rubber, epoxy rubber, polyurethane,acrylic, among the others now known or later developed. This sealant canhave a volume shrinkage of 0.5%-2% during curing (including heat curing,UV curing, moisture curing, among others now known or later developed)to keep the glass plate 1340 and the mirror 1310 stuck together tightlyafter curing to obtain a better encapsulation. The curing method isselected depending on the characteristics of the sealant.

Depending on different types of adhesives used, at least two examplepreparation processes are presented hereinafter to encapsulatepre-assembled ECDs into a rearview mirror including both flat and curvedones.

Method A: Optical Transparent Adhesives.

1. Prepare the materials: Cut the adhesive and ECD into the desiredshape and size with a die cutting machine or a laser machine or othersknown in the arts. Set the right instrument parameters to ensure thatthe cutting process is performed smoothly. The setting parameters forboth a die cutting machine and a laser machine are determined based onthe thickness and characteristics of the materials. For example, whenusing an optical clear adhesive with a thickness of 100 urn, the movingspeed of the laser machine can range, for example, from 1 mm/s to 600mm/s. The energy of the laser machine can range, for example, from 1 wto 500 w. The frequency of the laser machine can range, for example,from 1 Hz to 10000 Hz.

1.1 Thermoforming of the materials: To make a curved rearview mirror,the electrochromic thin film device can be first thermally bent into acurved shape with a certain curvature (curvature radius can range, forexample, from 50 mm to infinity) in an oven at 50° C. to 200° C. for 5min to 30 min using a mold conforming to the shape and curvature of thecurved surface with or without vacuum depending on the hardness of themold (as shown in FIGS. 14A and 14B). This step can help make step 2below easier since the thermally bent ECD can remain the same curvatureas the glass/mirror during the operation. However, because the ECD inthis disclosure is flexible and can be bent easily to fit to the surfacewith any shape and curvature, this step is optional to make curvedrearview mirrors with optical transparent adhesives. For a flat rearviewmirror, this step can be omitted.

2. Stick the adhesives to the glass/mirror (half-cell): Depending ondifferent states (liquid or solid) of the used adhesives, the procedurecan vary. For solid or sticky adhesives, a rolling method (see section2.1 below for details) or a vertical pressing method (see section 2.2below for details) is used to apply the adhesives to the surface ofglass or mirror. To prepare the flat rearview mirrors, it is easier toperform. To prepare the curved ones, customized tools may be used toassist the process, including but not limited to tools with the samecurvature as the one from the glass/mirror. For liquid adhesives, themachines used to dispense the liquid adhesives onto the surface, forexample, include dispenser, spraying gun, screen printing machine,coating machine, among others known in the arts. After dispensing theliquid adhesives, a vertical pressing method is normally adopted.

2.1 A rolling method: FIG. 15 is a diagram showing a process scheme forforming a rearview mirror according to one example embodiment. Fix thesurface of the glass or mirror (including the flat, curved and sphericalsurfaces, among the others known in the arts) on the special fixture ofthe rolling platform with a mold made from materials which are not ashard as steel (example materials include, but not be limited to, rubber,silica gel, polyurethane, polyacrylate, polyester, epoxy, among othersknown in the arts). The mold is customized according to the curvature ofthe glass/mirror when it comes to curved samples. Generally, the Shorehardness of the mold is more than 50. The curvature deviation betweenthe roller and the glass/mirror may be less than 10%. Attach the edge ofthe transparent adhesive to the edge of the glass. The edges of theadhesive layers can be flush with or beyond edges of the ECD accordingto FIG. 13B and FIG. 13C. The transparent adhesive includes, but notlimited to, hot melt adhesive, optical transparent adhesive, amongothers known in the arts, and its thickness may range, for example, from10 um to 500 um. The thickness of the glass may range, for example, from0.5 mm to 1.8 mm. The adhesive and the surface of the glass or mirrorare pressed by a roller as shown in FIGS. 16A and 16B, which is made bymaterials not as hard as steel, (including, but not limited to berubber, silica gel, polyurethane, polyacrylate, polyester, epoxy, amongothers known in the arts.). The roller is customized according to thecurvature of the glass/mirror. The Shore hardness of the roller iscommonly less than 100. The curvature deviation between the roller andthe glass/mirror may be less than 10%. During the rolling process, thepressure applied on both the adhesive layer and glass/mirror may range,for example from 100 Pa to 1000 kPa.

2.2 A vertical pressing method: FIG. 17 is a diagram showing anotherprocess scheme for forming a rearview mirror according to one exampleembodiment. Fix the glass or mirror (including the flat, curved andspherical ones) onto a mold with curvature determined based on theglass/mirror. The deviation between the curvature radius from the moldand the one from the glass/mirror may range, for example, from 0 mm to100 mm. Fix the adhesive onto another special mold which curvature isdesigned based on the mirror/glass. The deviation between the curvatureradius from the mold and the one from the glass/mirror may range, forexample, from 0 mm to 500 mm. The mold with the adhesive and the onewith the mirror/glass are separated and held by a machine to avoid anycontact before the pressing process. After the vacuum reaches the setnumber, normally more than 95%, the mold with the adhesive is pressedonto the mold with the glass/mirror by the engine or gear of thepressing machine for 5 s-15 min. During the pressing process, thepressure applied may range, for example, from 1 kPa to 1000 kPa.

3. Stick the ECD to the glass/mirror (the other half-cell): ECD isadhered to the adhesive layer which is already adhered to theglass/mirror as described in step 2. Example methods used for this stepmay include, but not be limited to rolling, vertical pressing, amongothers known in the arts.

3.1 A rolling method: FIG. 18 is a diagram showing a process scheme forforming a rearview mirror according to one example embodiment. Fix theglass or mirror with adhesive on the surface (including the flat, curvedand spherical surfaces) on the special fixture of the rolling platformwith a mold made from materials which are not as hard as steel (Examplematerials include, but not limited to, rubber, silica gel, polyurethane,polyacrylate, polyester, epoxy, among others known in the arts.). Themold is customized according to the curvature of the glass/mirror.Commonly the Shore hardness of the mold is more than 50. Normally thecurvature deviation between the roller and the glass/mirror may be lessthan 10%. Align the edge of the ECD with the edge of the adhesive on thesurface of the glass or mirror. The ECD and the adhesive on the surfaceof the glass or mirror are pressed by a roller as shown in FIGS. 16A and16B. The roller is made by materials not as hard as steel (including,but not limited to be rubber, silica gel, polyurethane, polyacrylate,polyester, epoxy, among others known in the arts.). The roller iscustomized according to the curvature of the glass/mirror. The Shorehardness of the roller is commonly less than 100. The curvaturedeviation between the roller and the glass/mirror may be less than 10%.During the rolling process, the pressure applied on both the adhesivelayer and glass/mirror may range, for example from 100 Pa to 100 kPa).

3.2 A vertical pressing method: FIG. 19 is a diagram showing anotherprocess scheme for forming a rearview mirror according to one exampleembodiment. Fix the glass or mirror with adhesive on the surface(including the flat, curved and spherical ones) onto a mold withcurvature determined based on the glass/mirror. The deviation betweenthe curvature radius of the mold and the one of the glass/mirror mayrange, for example, from 0 mm to 100 mm. Fix the ECD onto anotherspecial mold which curvature is designed based on the mirror/glass. Thedeviation between the curvature radius of the mold and the one of theglass/mirror may range, for example, from 0 mm to 500 mm. The mold withthe ECD and the one with the mirror/glass with the adhesive on thesurface are separated and held by a machine to avoid any contact beforethe pressing process starts. After the vacuum reaches the set number,normally more than 95%, the mold with the adhesive is pressed onto theglass/mirror held by the other mold for 5 s-15 min. During the pressingprocess, the pressure applied may range, for example, from 1 kPa to 1000kPa.

4. Pack the two half cells together: FIG. 20 is a diagram showinganother process scheme for forming a rearview mirror according to oneexample embodiment. One half-cell is made via step 1 and the other oneis made via step 2. For this step, the two half cells may be packedtogether via different methods, including but not be limited to pressingwith or without heating and with or without vacuum. Fix the glass ormirror with adhesive on the surface (including the flat, curved andspherical ones) of a mold which curvature is determined based on theglass/mirror. The deviation between the curvature radius of the mold andthe one of the glass/mirror may range from 0 mm to 100 mm. Fix themirror/glass with ECD stuck on the surface of another special mold whichcurvature is also designed based on the mirror/glass. The deviationbetween the curvature radius of the mold and the one of the glass/mirrormay range from 0 mm to 500 mm. The mold with the adhesive and the onewith the mirror/glass are separated and held by a machine to avoid anycontact before the pressing process. After the vacuum reaches the setnumber, normally more than 95%, the mold with the adhesive is pressedonto the glass/mirror held by the other mold for 5 second to 15 minutes.During the pressing process, the pressure applied is normally 1 kPa- to1000 kPa.

5. Encapsulate the edge with proper sealant: This step can be done afterthe first 4 steps (described in step 5.1) or it can be integrated intoone of them depending on the various aspects, including the propertiesof the sealant, of the edge of the glass (described in 5.2). If theviscosity of the sealant is low, normally range from 100 cps to 10,000cps, method 5.1 is adopted. When the viscosity of the sealant is veryhigh, normally range from 100,000 cps to 2,000,000 cps, then method 5.2is adopted. When the viscosity is in the middle (neither too high nortoo low), then either method can be used.

5.1 FIG. 21 is a schematic diagram showing a sealing process accordingto one example embodiment. As shown in FIG. 21, after the first foursteps, encapsulant is evenly dripped onto the edge between the mirror1310 and the glass 1340 by an appropriate machine including but notlimited to glue dispenser, holt-melt adhesive dispenser, among othersknown in the arts. The amount of the encapsulant is well controlled toavoid bubbles and overflow. The flow rate may range, for example, from0.001 mL/min to 50 mL/min. The flow rate is determined by the thicknessand width of the encapsulant. The thickness of the encapsulant commonlyranges, for example, from 0.1 mm to 3 mm. The width of the encapsulantcommonly ranges, for example, from 0.01 mm to 5 mm. The diameter of thedispenser needle may range, for example, from 0.01 mm to 5 mm. Afterbeing dispensed, the encapsulant is cured via an appropriate curingmethod, including but not limited to radiation (e.g. UV) curing, heatcuring, moisture curing, among others known in the arts.

5.2 The encapsulant dispensing can also be integrated into one of thestep 2 to step 4. The encapsulant is evenly dripped onto the edge of themirror or the glass by an appropriate machine including but not limitedto glue dispenser, holt-melt adhesive dispenser, among others known inthe arts. For example, as shown in FIGS. 22A and 22B, the encapsulant isdispensed after step 2 which means after the adhesive is adhered to thesurface of glass/mirror, the encapsulant is distributed evenly alongwith edge of glass/mirror. Then the steps that follow step 2 can beperformed. Another sample is shown in FIG. 23, the encapsulant isdispensed after step 3 which means after the ECD is adhered to thesurface of glass/mirror, the encapsulant is distributed evenly alongwith edge of glass/mirror. Then the steps that follow step 3 can beperformed.

Method B: Hot Melting Adhesives

1. Prepare the materials: Cut the adhesive and ECD into a desired shapeand size with a die cutting machine or a laser machine or others knownin the art. Set the right instrument parameters to ensure that thecutting process is performed smoothly. The thickness of the hot meltingadhesives may range, for example, from 0.01 mm to 5 mm.

2. Thermoforming of the materials: To prepare a flat rearview mirror,this step is not necessary. When it comes to a curved rearview mirror,thermoforming is optional, but helpful to keep the ECD at a fixed shapeto eliminate the defect possibility caused by the change of shape. Toprepare a curved rearview mirror, the electrochromic thin film device isfirst thermally bent into a curved shape with a certain curvature in anoven at the temperature ranging from 50° C. to 200° C. for 5-30 minusing a mold conforming to the shape and curvature of the curvedsurface. The radius for the curvature can range, for example, from 50 mmto infinity.

3. Stack the adhesive, mirror, glass together: Stack the adhesive,mirror and glass together layer by layer in an order shown in FIGS. 13Aand 13B. Then melt and cure the adhesive. After this step, the fivelayers are integrated into one single piece.

4. Encapsulate the edge with sealant: this step can be performed by thesame way as step 5 in method A.

Embodiment 8: Use Method a to Make a Curved EC Mirror with a CurvatureRadius of 1200 mm

800. Prepare the materials with a laser machine. To cut an optical clearadhesive with a thickness of 100 μm, the moving speed of the lasermachine is set to be 100 mm/s, laser power is set to be 10 W, and thefrequency is set to be 100 Hz. The height of the laser over the adhesivelayer is 0.2 cm.

810. Thermoforming step: Put the electrochromic thin film device into acustomized mold (both upside and downside mold) with a curvature radiusof 1200 mm, then set the temperature of the oven as 100° C. for 15 min,then take them out and cool down to the room temperature. Theelectrochromic thin film device is thermally bent into a curved shapewith a certain curvature radius of 1200 mm.

820. Stick the adhesive to the glass (half-cell) with a rolling method:Fix the surface of the glass/mirror on the special fixture of therolling platform with a mold made by polyurethane. The mold iscustomized with a curvature radius of 1200 mm which is the same as theglass/mirror. The Shore hardness of the mold is 85. Align the edge ofthe transparent adhesive (with a thickness of 150 μm) with the edge ofthe glass (with the thickness of 1.1 mm). The transparent adhesive andthe surface of the glass are pressed by a roller made by rubber with thesame curvature as the one from the glass. The Shore hardness of theroller is 65. During the rolling process, the pressure applied on theadhesive layer and glass/mirror is 1 kPa.

830. Stick the ECD to the mirror (half-cell) with a rolling method: Fixthe mirror with adhesive on the surface of the special fixture from therolling platform with a mold which is made by polyurethane and iscustomized with the curvature radius of 1200 mm. The Shore hardness ofthe mold is 85. Align the edge of the ECD with the edge of thetransparent adhesive, then the ECD and the adhesive on the surface ofthe mirror are pressed by a roller made by rubber with the curvatureradius of 1200 mm. The Shore hardness of the roller is 65. During therolling process, the pressure applied on the adhesive layer andglass/mirror is 10 kPa.

840. Pack the two half cells together: Fix the glass with adhesive onthe surface of a mold with the curvature radius of 1250 mm. Fix themirror with ECD on the surface of another special mold with a curvatureradius of 1150 mm. The mold with the adhesive and the one with themirror/glass are separated and held by a machine to avoid any contactbefore the pressing process. After vacuum reaches 99.5%, the mold withthe adhesive is pressed onto the glass/mirror held by the other mold for1 min. During the pressing process, pressure applied is 100 kPa.

850. Encapsulate the edge with UV curing sealant: UV curing encapsulantis evenly dripped onto the edge between the mirror and the glass by aglue dispenser. The flow rate is 0.5 mL/min and the diameter of thedispenser needle is 0.5 mm. After dispensing, the encapsulant is curedvia UV curing, with an energy of 2000 mJ/cm².

Embodiment 9: Use Method a to Make a Curved EC Mirror with a CurvatureRadius of 1200 mm

900. Prepare the materials with a laser machine. The same as Embodiment8.

910. Stick the adhesive to the glass/mirror (half-cell) with a verticalpressing method: Fix the glass onto a mold which curvature radius is1250 mm. Fix the adhesive onto another special mold which curvatureradius is 1150 mm. The mold with the adhesive and the one with the glassare separated and held by a machine to avoid any contact before thepressing process. After vacuum reaches more than 99.5%, the mold withthe adhesive is pressed onto the glass/mirror held by the other mold for30 s. During the pressing process, pressure applied is 100 kPa.

920. Stick the ECD to the mirror (half-cell) with a vertical pressingmethod: Fix the mirror with adhesive on the surface onto a mold whichcurvature radius is 1250 mm. Fix the ECD onto another special mold whichcurvature radius is 1150 mm. The mold with the ECD and the one with themirror with adhesive on the surface are separated and held by a machineto avoid any contact before the pressing process. After vacuum reachesmore than 99.5%, the mold with the adhesive is pressed onto the mirrorheld by the other mold for 30 s. During the pressing process, pressureapplied is 100 kPa.

930. Pack the two half cells together: The same as embodiment 8.

940. Encapsulate the edge with UV curing sealant: The same as embodiment8.

Embodiment 10: Make a Flat EC Mirror with Method B

1000. Prepare the materials with a die cutting machine. Set theparameters of a die cutting machine as follow to cut PVB: the customizedmold is used which shape is determined based on the shape of the glass,the pressing power is set to be 5 t. The height of the mold over theadhesive layer is 1.0 cm.

1010. Stack the adhesive, mirror, glass together (FIG. 24) and put theminto a hot-pressing machine which has the function of vacuum, heatingand pressure. Set the vacuum as 99%, temperature of 140° C. and time for30 min with a pressure of 6 bar. After this step, the 5 layers arecombined.

1020. Encapsulate the edge with proper sealant: The same as embodiment8.

Embodiment 11: Make a Curved EC Mirror with Method B

1100. Prepare the materials with a laser machine. Set the parameters ofa laser machine as follow to cut PVB, the moving speed of the laser is100 mm/s, power is 100 W, and the frequency is 100 Hz. The height of thelaser over the adhesive layer is 0.5 cm.

1110. Thermoforming of the materials: Fix the PVB onto the customizedmold with a curvature radius of 1200 mm. And put them together into anoven of 100° C. for 15 min. Then take them out and cool down to the roomtemperature. PVB has the same curvature as the mold.

1120. Stack the adhesive, mirror, glass together and then do the same asin 1010 of embodiment 10.

1130. Encapsulate the edge with proper sealant: The same as embodiment1.

In some embodiments, in the structures shown in FIG. 24, a thickness ofthe glass and the mirror is about 0.5-1.8 mm; a thickness of the PVB/EVAadhesive is about 0.05-0.5 mm; as thickness of the ECD is about 0.1-1mm.

In some embodiments, the techniques disclosed herein allows to form allsolid-state flexible thin-film ECDs. Both electrochromic and ion-storagelayers are deposited on the flexible plastic substrates to form thinfilms. The precursor of the electrolyte is coated on top of either thinfilm. Then, the other thin film is laminated on the top to form alaminated structure. The laminated structure is placed under the UVlight or heated at 80-120° C. to induce the crosslinking of theprecursor and form a solid-state electrolyte which further adheres theelectrochromic and ion storage layer together. The pre-assembledthin-film ECDs can be then easily applied to different glass surfaceswith different sizes and curvatures. Moreover, compared with thetraditional glass-based ECDs with gel or liquid electrolytes, the ECDsare lighter without the need for the bulky sealing.

To overcome the disadvantages of the conventional ECDs, disclosed is anew configuration of an electrochromic rearview mirror that has a thinfilm ECD. In this thin film ECD, both electrochromic layers and ionstorage layers are fabricated on flexible substrates such aspolyethylene terephthalate (PET) substrates via a high-throughputprocessing method, e.g., roll-to-roll processing and laminated with theprecursor of the electrolyte interposed therebetween. The precursorelectrolyte is crosslinked via the UV irradiation or heating which formssolid-state electrolyte and further adheres the electrochromic and ionstorage layer together to form a pre-assembled thin film device.

In some embodiments, both the electrochromic layers and ion storagelayers are coated on flexible ITO/PET substrates via spray coating, orspin coating, or slot-die coating or any other solution compatiblecoating techniques now known or later developed, and then laminated withthe precursor of the electrolyte in the middle through roll formingprocess at a temperature ranging from 20-100° C., a speed ranging from0.1-5 m/min, and a pressure ranging from 0.01-5 MPa. The roller used inthis process can be made of rubber, stainless steel, ceramic, aluminum,or any other materials that can sustain high temperature (200° C.) andpressure (10 MPa). The precursor of the electrolyte in the laminatedthin film was cured through either UV light with energy ranging from50-10000 mJ cm-2 or heating at 80-120° C. oven. The crosslinking of theelectrolyte forms a solid-state electrolyte and adheres both theelectrochromic and ion storage layer together, resulting in an all-solidstate thin-film device. This as-assembled flexible solid-state thin filmECD can also be easily applied to fabricate other window-type devicesand can easily transform any glasses with/without curvatures intoelectrochromic smart glasses.

In some embodiment, the electrochromic layer can be one of thesematerials: tungsten oxide (WO3), poly(decylviologen) and itsderivatives, polyaniline and its derivatives, all kinds ofelectrochromic conjugated polymers such as polypyrrole and itsderivatives, polythiophene and its derivatives,poly(3,4-ethylenedioxythiophene) and its derivatives,poly(propylenedioxythiophene) and its derivatives, polyfurane and itsderivatives, polyfluorene and its derivatives, polycarbazole and itsderivatives, and their copolymers, or their copolymers containing acertain ratio of acceptor units, such as benzothiadiazole,benzoselenadiazole, benzooxazole, benzotriazole, benzoimidazole,quinoxalines, and diketopyrrolopyrroles, and others now known or laterdeveloped. The electrochromic layer has the thicknesses of 1-1500 nm.The ion storage layer can be nitrioxyl based radical polymer, NiOx,PEDOT, etc. with thicknesses in the range of 1-1000 nm.

These techniques provide an easy way to fabricate flat and curvedauto-dimming rearview mirrors with solid-state flexible thin film ECDs.Compared with the conventional materials and encapsulation methods, theall-solid-state ECDs are safer as nothing will leak when the glass isbroken. Further, the transparent optical glue can help improve theexplosion protection. In addition, the all-solid-state ECDs and theproposed processes make it possible to use thinner glass and mirror tohelp reduce the product weights.

The disclosed processes make the industrial production of the anti-glarerearview mirror more manufacturing friendly and cost efficient withimproved production yield and reduced waste and defect rate.

Other than anti-glare rearview mirrors disclosed in this disclosure, thepre-assembled flexible solid-state thin film ECD can also be easilyapplied to fabricate other window-type devices and can easily transformany glasses with/without curvatures into electrochromic smart glasses.

The foregoing description of the present invention has been provided forthe purposes of illustration and description. It is not intended to beexhaustive or to limit the invention to the precise forms disclosed. Thebreadth and scope of the present invention should not be limited by anyof the above-described exemplary embodiments. Many modifications andvariations will be apparent to the practitioner skilled in the art. Themodifications and variations include any relevant combination of thedisclosed features. The embodiments were chosen and described in orderto best explain the principles of the invention and its practicalapplication, thereby enabling others skilled in the art to understandthe invention for various embodiments and with various modificationsthat are suited to the particular use contemplated. It is intended thatthe scope of the invention be defined by the following claims and theirequivalence.

What is claimed is:
 1. An electrochromic apparatus, comprising: a firstglass; a first adhesive layer disposed on the first glass; a secondglass; a second adhesive layer disposed on the second glass; asolid-state electrochromic device (ECD) interposed between the firstadhesive layer and the second adhesive layer; and a sealant disposed atedges of the first glass and the second glass to seal the ECD, the firstadhesive layer and the second adhesive layer being disposed between thefirst glass and the second glass, wherein, the first adhesive layer andthe second adhesive layer are optically transparent; edges of theadhesive layers are flush with or beyond edges of the ECD; and thesealant is adhesive and waterproof.
 2. The electrochromic apparatus ofclaim 1, wherein the solid-state electrochromic device comprises a solidelectrolyte layer containing solid electrolyte polymers having a polymerbackbone structure that includes no amine group, wherein the solidelectrolyte polymers includes: (a) ion conducting polymers copolymerizedwith monomers or oligomers, wherein the monomers or oligomers haveplasticizing moieties as a side chain; (b) ion conducting polymerscovalently linked with plasticizing linear polymers that have a glasstransition temperature less than −20° C.; (c) ion conducting polymerscovalently linked with plasticizing polymer blocks that haveplasticizing groups as side chains; or (d) brush copolymers with sidechains of one or more ion-conducting species and one or morenon-miscible groups.
 3. The electrochromic apparatus of claim 1, whereinone surface of the second glass has a reflective layer.
 4. Theelectrochromic apparatus of claim 1, wherein the first adhesive layerand the second adhesive layer include one or more of liquid opticalclear adhesives, resin optical clear adhesives, solid optical adhesives,and hot melting adhesives.
 5. The electrochromic apparatus of claim 4,wherein the hot melting adhesives include one or more of an ethylenevinyl acetate membrane, and a polyvinyl butyral membrane.
 6. Theelectrochromic apparatus of claim 1, wherein the sealant includes one ormore of butyl rubber, epoxy rubber, polyurethane, and acrylic.
 7. Theelectrochromic apparatus of claim 3, wherein the reflective layer ismade by one or more of a pure metal, an alloy, a non-metallic material,and a hybrid material.
 8. The electrochromic apparatus of claim 2,wherein the solid-state electrochromic device further comprises a firstflexible substrate; a first transparent electrode disposed on the firstflexible substrate; an electrochromic layer disposed on the firsttransparent electrode, wherein the solid electrolyte layer is disposedon the electrochromic layer; an ion storage layer disposed on the solidelectrolyte layer; a second transparent electrode disposed on the ionstorage layer; and a second flexible substrate disposed on the secondtransparent electrode.
 9. The electrochromic apparatus of claim 8,wherein the first flexible substrate and the second flexible substrateinclude one of polyethylene terephthalate, cyclic olefin copolymer, ortriacetate cellulose.
 10. The electrochromic apparatus of claim 8,wherein the first transparent electrode and the second transparentelectrode include indium-tin oxide (ITO), aluminum zinc oxide (AZO),fluorine doped tin oxide (FTO), silver nanowires, graphene, carbonnanotube, metal mesh based transparent conductive electrodes, orsilver-nanoparticle ink.
 11. The electrochromic apparatus of claim 8,wherein the ion storage layer includes one or more oxides of metalelements in Group 4-12, or a mixture of the oxides, or one of the oxidesdoped by any other metal oxides.
 12. The electrochromic apparatus ofclaim 11, wherein the metal oxides include the oxides of Ti, V, Nb, Ta,Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu, or Zn.
 13. The electrochromicapparatus of claim 8, wherein the ion storage layer includes atransition-metal complex.
 14. The electrochromic apparatus of claim 8,wherein the ion storage layer includes one or more of redox-activepolymers including redox active nitroxyl or galvinoxyl radical polymers,or conjugated polymers.
 15. The electrochromic apparatus of claim 8,wherein the electrochromic layer includes one or more of WO₃,poly(decylviologen) and its derivatives, polyaniline and itsderivatives, electrochromic conjugated polymers including polypyrroleand its derivatives, polythiophene and its derivatives,poly(3,4-ethylenedioxythiophene) and its derivatives,poly(propylenedioxythiophene) and its derivatives, polyfurane and itsderivatives, polyfluorene and its derivatives, polycarbazole and itsderivatives, and copolymers thereof, or the copolymers containingacceptor units including benzothiadiazole, benzoselenadiazole,benzooxazole, benzotriazole, benzoimidazole, quinoxalines, ordiketopyrrolopyrroles.
 16. A method for preparing an electrochromicapparatus, comprises: applying a first adhesive layer to a first glassto form a first half-cell and applying a second adhesive layer to asecond glass to form a second half-cell; sticking a solid-stateelectrochromic device (ECD) to the first half-cell to form an ECD-firsthalf cell; packing the ECD-first half cell and the second half celltogether; applying a sealant to the ECD-first half cell or the secondhalf cell; curing the sealant to form the electrochromic apparatus. 17.The method of claim 16, wherein applying the sealant to the ECD-firsthalf cell or the second half cell comprises: (a) applying the sealant toan end portion between the first glass and the second glass; or (b)applying the sealant to edges of one or both the ECD-first half cell andthe second half cell.
 18. A method for preparing an electrochromicapparatus, comprises: stacking a first glass, a first adhesive, asolid-state electrochromic device (ECD), a second adhesive, and a secondglass together layer by layer in a certain order; dripping a sealant toan end portion between the first glass and the second glass; and curingthe sealant to form the electrochromic apparatus.
 19. The method ofclaim 18, further comprising cutting the first adhesive layer, thesecond adhesive layer, and the ECD into predetermined shapes.
 20. Themethod of claim 18, further comprising thermally bending the ECD into acurved shape in an oven.